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Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies
P. Franz, C. Ambrus, A. Hauser, D. Chernyshov, M. Hostettler, J. Hauser, L. Keller, K. Krämer, H. Stoeckli-Evans, P. Pattison, H.-B. Bürgi and S. Decurtins
Journal of the American Chemical Society, 126 (50) (2004), p16472-16477
DOI:10.1021/ja0465451 | unige:3247 | Abstract | Article HTML | Article PDF
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The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2·zH2O (z = 12−16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K. |